EP3464437A1 - Fibre reinforcement of reactive foams obtained by a moulding foam method - Google Patents
Fibre reinforcement of reactive foams obtained by a moulding foam methodInfo
- Publication number
- EP3464437A1 EP3464437A1 EP17723145.3A EP17723145A EP3464437A1 EP 3464437 A1 EP3464437 A1 EP 3464437A1 EP 17723145 A EP17723145 A EP 17723145A EP 3464437 A1 EP3464437 A1 EP 3464437A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- fiber
- reactive
- foam
- layer
- reactive foam
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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Definitions
- the present invention relates to a shaped body made of reactive foam, wherein at least one fiber (F) is located partially within the shaped body, ie is enclosed by the reactive foam. The two ends of the respective fiber (F) not surrounded by the reactive foam thus protrude from one side of the corresponding shaped body.
- the reactive foam is produced by a foam molding process.
- Another object of the present invention is a panel comprising at least one such shaped body and at least one further layer (S1). Further objects of the present invention are methods for producing the shaped bodies according to the invention from reactive foam or the panels according to the invention and their use, for example as a rotor blade in wind turbines.
- WO 2006/125561 relates to a method for producing a reinforced cellular material, wherein in a first method step at least one hole is created in the cellular material extending from a first surface to a second surface of the cellular material. On the other side, the second surface of the cellular material, at least one fiber bundle is provided, this fiber bundle being pulled with a needle through the hole to the first side of the cellular material. However, before the needle grasps the fiber bundle, the needle is first pulled from the first side of the cellular material through the respective hole.
- the fiber bundle is partly located within the cellular material, since it fills the corresponding hole, in part the corresponding fiber bundle protrudes on the respective sides from the first and second surface of the cellular material.
- the method described in WO 2006/125561 can be used to produce sandwich-type components comprising a core of said cellular material and at least one fiber bundle. On the surfaces of this core, resin layers and fiber-reinforced resin layers may be applied to produce the actual sandwich-type component.
- the cellular material for forming the core of the sandwich-type component polyvinyl chlorides or polyurethanes, for example, can be used.
- a fiber bundle for example, carbon fibers, nylon fibers, glass fibers or polyester fibers in question.
- WO 2006/125561 does not disclose that reactive foams produced by a foam molding process are used as the cellular material for producing a foam Kerns can be used in a sandwich-like component.
- the sandwich-like components according to WO 2006/125561 are suitable for use in aircraft construction.
- WO 201 1/012587 relates to another process for producing a core with integrated bridge fibers for panels of composite materials.
- the core is made by partially or fully drawing through a bridle fiber provided on a surface of the respective cake by means of a needle through a so-called "cake" made of light material Foam, in particular be formed of a polyurethane foam.
- any type of single or multiple threads and other yarns can be used as the fibers.
- the cores thus produced may in turn be part of a panel of composite materials, wherein the core is surrounded on one or both sides by a resin matrix and combinations of resin matrices with fibers in a sandwich-like configuration.
- WO 201 1/012587 does not disclose that reactive foams produced by a foam molding process can be used to produce the corresponding core material.
- WO 2012/138445 relates to a method of making a composite core panel using a plurality of elongated strips of a low density cellular material. Between the respective strips a double-layered fiber mat is introduced which, by using resin, causes the individual strips to stick together to form the composite core panels.
- the cellular material of low density forming the elongated strips is selected according to WO 2012/138445 from balsa wood, elastic foams or fiber-reinforced composite foams.
- the double-layered fiber mats introduced between the individual strips may be, for example, a porous glass fiber mat.
- the resin used as the adhesive may be, for example, a polyester, an epoxy or a phenolic resin or a thermally activated thermoplastic, for example polypropylene or PET.
- WO 2012/138445 does not disclose that as a cellular material for the elongated strips, a reactive foam prepared by a foam molding process can also be used. Nor is it disclosed that single fibers or fiber bundles can be incorporated into the cellular material for reinforcement. According to WO 2012/138445 exclusively fiber mats are used for this purpose, which also represent a connecting member in the context of an adhesive bond of the individual strips by means of resin to obtain the core material.
- GB-A-2 455 044 discloses a method for producing a multilayer composite article, wherein in a first method step a plurality of pellets of thermoplastic material and a blowing agent are provided.
- the thermoplastic material is a mixture of polystyrene (PS) and polyphenylene oxide (PPO) containing at least 20 to 70 weight percent PPO.
- PS polystyrene
- PPO polyphenylene oxide
- the pellets are expanded and welded in a third step in a mold to form a closed-cell foam of the thermoplastic material into a shaped body, wherein the closed-cell foam assumes the shape of the mold.
- a layer of fiber-reinforced material is applied to the surface of the closed-cell foam, the attachment of the respective surfaces being carried out using an epoxy resin.
- GB-A-2 455 044 does not disclose that a fibrous material can be incorporated into the core of the multilayer composite article.
- a similar method or an analogous multilayer composite article (as in GB-A 2 455 044) is also disclosed in WO 2009/047483.
- These multilayer composite articles are suitable, for example, for use as rotor blades (in wind turbines) or as boat hulls.
- US Pat. No. 7,201,625 discloses a method for the production of foam products and the foam products as such, which can be used, for example, in sports as a surfboard.
- the core of the foam product forms a particle foam, for example based on a polystyrene foam.
- This particle foam is produced in a special form, wherein a plastic outer skin encloses the particle foam.
- the plastic outer skin can be, for example, a polyethylene film.
- US Pat. No. 7,201,625 does not disclose that fibers for reinforcing the material can be contained in the particle foam.
- US-B 6,767,623 discloses sandwich panels comprising a core layer of polypropylene particle foam based on particles having a particle size in the range of 2 to 8 mm and a bulk density in the range of 10 to 100 g / l. Furthermore, the sandwich panels comprise two cover layers of fiber-reinforced polypropylene, wherein the individual cover layers are arranged around the core, that a sandwich is formed. Optionally, further layers may be included for decorative purposes in the sandwich panels.
- the cover layers may contain glass fibers or other polymer fibers.
- EP-A 2 420 531 discloses extruded foams based on a polymer such as polystyrene, in which at least one mineral filler with a particle size of ⁇ 10 ⁇ m and at least one nucleating agent are present. These extrusion foams are characterized by their improved rigidity. Furthermore, a corresponding extrusion process for producing such extruded foams based on polystyrene is described. The extrusion foams may be closed cell. However, EP-A 2 480 531 does not describe that the extrusion foams contain fibers.
- WO 2005/056653 relates to particle foam moldings made of expandable polymer granules containing filler.
- the particle foam moldings are obtainable by welding prefoamed foam particles of expandable, filler-containing, thermoplastic polymer granules, wherein the particle foam has a density in the range of 8 to 300 g / l.
- the thermoplastic polymer granules are in particular a styrene polymer.
- filler powdery inorganic substances, metal, chalk, aluminum hydroxide, calcium carbonate or alumina or spherical or fibrous inorganic substances such as glass beads, glass fibers or carbon fibers can be used.
- US 3,030,256 describes laminated panels and a method for their production.
- the panels include a core material into which fiber bundles are introduced and surface materials.
- the core materials are foamed plastic and expanded plastic.
- the fibers are located within a fiber region within the foam. A first fiber region protrudes from the first side of the molding, a second fiber region protrudes from the second side of the molding.
- US 6,187,411 relates to reinforced sandwich panels comprising a foam core material having a fibrous layer on both sides and fibers which are pierced through the outer fibrous layers and the foam.
- Foamed core materials are polyurethanes, phenols and isocyanates.
- US 2010/0196652 relates to quasi-isotropic sandwich structures comprising a core material surrounded by fiber mats with glass fiber rovings pricking into the fiber mats and the core material.
- foams various foams, such as polyurethane, polyisocyanurate, phenols, polystyrene, PEI, polyethylene, polypropylene and the like are described.
- a disadvantage of the composite materials described in US Pat. No. 3,030,256, US Pat. No. 6,187,411 and US 2010/0196652 is that they frequently have a high resin uptake.
- reactive foams there are a variety of different manufacturing processes, materials and resulting properties.
- the object underlying the present invention is to provide new fiber-reinforced moldings or panels.
- a molded body of reactive foam wherein at least one fiber (F) is located with a fiber region (FB2) within the molding and is enclosed by the reactive foam, while a fiber region (FB1) of the fiber (F) from a protruding first side of the molded body and a fiber portion (FB3) of the fiber (F) protrudes from a second side of the shaped body, wherein the reactive foam is produced by a foam molding process, wherein the fiber (F) at an angle ⁇ of 10 to 70 ° relative to Thickness direction (d) of the shaped body is introduced into the reactive foam and wherein the shaped body is obtainable by a process comprising the steps a) to f): a) optionally applying at least one layer (S2) on at least one side of the reactive foam, b) production from a hole per fiber (F) in the reactive foam and optionally the layer (S2), wherein the hole of a c) providing at least one fiber (F) on the second side of the
- the subject of the present invention is also a shaped body of reactive foam in which at least one fiber (F) is located within the shaped body with a fiber region (FB2) and is enclosed by the reactive foam, while a fiber region (FB1) of the fiber (F) consists of a protrudes first side of the shaped body and a fiber region (FB3) of the fiber (F) protrudes from a second side of the shaped body, wherein the reactive foam is prepared by a foam molding process.
- the reactive foam is obtainable by a foam molding process.
- the moldings according to the invention are advantageously characterized by a low resin absorption and at the same time good interfacial bonding, wherein the low resin absorption is due in particular to the reactive foam produced by a foam molding process. This effect is of particular importance when the shaped bodies according to the invention are further processed into the panels according to the invention.
- the fibers can advantageously be introduced first of all dry and / or by mechanical processes into the reactive foam.
- the fibers or fiber bundles are not flush to the respective reactive foam surfaces, but deposited with supernatant and thus allow an improved connection or a direct connection with the corresponding cover layers in the panel according to the invention. This is the case in particular if, as cover layer, according to the invention at least one further layer (S1) is applied to the shaped bodies according to the invention with the formation of a panel.
- two layers (S1) which may be the same or different, are applied.
- two identical layers (S1) in particular two identical fiber-reinforced resin layers, are applied to opposite sides of the molded body according to the invention to form a panel according to the invention.
- Such panels are also referred to as “sandwich materials", wherein the shaped body according to the invention can also be referred to as "core material”.
- the panels of the invention are thus characterized by a low resin absorption in conjunction with a good peel strength and a good shear stiffness and a high shear modulus. Furthermore, high strength and stiffness properties are specifically adjusted by the choice of fiber types, their proportion and arrangement.
- the effect of a low resin absorption is important because when using such panels (sandwich materials) often the goal is that the structural properties should be increased with the lowest possible weight.
- the resin absorption of the shaped body (core material) contributes to the overall weight.
- the resin absorption can be reduced, as a result of which weight and costs can be saved.
- the closed surface of the reactive foam can be considered.
- the reactive foam After the reactive foam is produced by a foam molding process, there is typically a sealed (closed) surface of high surface quality, characterized by minimal resin uptake and a density gradient from the core of the reactive foam towards the surface, the density being from the core of the reactive foam increases to its surface.
- a reactive foam having a density gradient wherein the density increases from the core of the reactive foam towards its surface is also referred to as integral foam.
- closed surface is understood to mean the following: The closed surface is evaluated by light or electron microscopic images defined as: (1 - area fraction of the opened foam cells) / total surface area> 30%, preferably> 50%, more preferably> 80%, in particular> 95%.
- a further advantage of the shaped bodies or panels according to the invention is that due to the use of reactive foams or the production associated therewith, the attachment of integrated structures such as slots or holes on the surfaces of the shaped bodies as well as the further processing of the shaped bodies is relatively simple.
- shaping steps such as thermoforming or machining integrate.
- such structures are often used in draping curved structures (deep slits), improving workability by liquid resin processes such as vacuum infusion (holes), and accelerating the aforementioned processing (shallow slits) when using such moldings (core materials).
- the introduced structures also preferably have a closed surface and thus a very low or even no resin absorption.
- layers (S2) can be applied to the reactive foam during or after production. Such layers (S2) improve the overall cohesion of the reactive foam or the molding according to the invention.
- the resin (cover) layer is applied by liquid injection or liquid infusion process, in which the fibers can be impregnated with resin during processing and the mechanical properties can be improved. In addition, this can be cost savings.
- the shaped body comprises a reactive foam and at least one fiber (F).
- the fiber (F) contained in the shaped body is a single fiber or a fiber bundle, preferably a fiber bundle.
- fiber (F) are all known in the art materials that can form fibers.
- the fiber (F) is an organic, inorganic, metallic, ceramic fiber or a combination preferably a polymeric fiber, basalt fiber, glass fiber, carbon fiber or natural fiber, more preferably a polyaramid fiber, glass fiber, basalt fiber or carbon fiber
- a polymeric fiber is preferably a fiber of polyester, polyamide, polyaramid, polyethylene, polyurethane, polyvinyl chloride, polyimide and / or Polyamide-imide
- a natural fiber is preferably a fiber of sisal, hemp, flax, bamboo, coconut and / or jute.
- fiber bundles are used.
- the fiber bundles are composed of several individual fibers (filaments).
- the number of single fibers per bundle is at least 10, preferably 100 to 100,000, more preferably 300 to 10,000 in glass fibers and 1,000 to 50,000 in carbon fibers, and more preferably 500 to 5,000 in glass fibers and 2,000 to 20,000 in carbon fibers.
- the at least one fiber (F) with a fiber region (FB2) is located inside the molding and is enclosed by the reactive foam, while a fiber region (FB1) of the fiber (F) protrudes from a first side of the molding and a fiber region (FB3) the fiber (F) protrudes from a second side of the shaped body.
- the fiber region (FB1), the fiber region (FB2) and the fiber region (FB3) can each make up an arbitrary fraction of the total length of the fiber (F).
- the fiber region (FB1) and the fiber region (FB3) each independently form 1 to 45%, preferably 2 to 40% and more preferably 5 to 30%, and the fiber region (FB2) 10 to 98%, preferably 20 to 96%, more preferably 40 to 90% of the total length of the fiber (F).
- the first side of the shaped body, from which the fiber region (FB1) of the fiber (F) protrudes faces the second side of the shaped body, from which the fiber region (FB3) of the fiber (F) protrudes.
- the fiber (F) is introduced at an angle ⁇ of 10 to 70 ° relative to the thickness direction (d) of the molding or to the orthogonal (the surface) of the first side (2) of the molding in the molding.
- the fiber (F) is preferably introduced into the reactive foam at an angle ⁇ of 30 to 60 °, preferably 30 to 50 °, more preferably 30 to 45 °, in particular 45 °, relative to the thickness direction (d) of the shaped body.
- angle ⁇ can assume any values from 0 to 90 °.
- the fiber (F) is then at an angle ⁇ of 0 to 60 °, preferably from 0 to 50 °, more preferably from 0 to 15 ° or from 10 to 70 °, preferably from 30 to 60 °, more preferably from 30 to 50 °, even more preferably from 30 to 45 °, in particular from 45 °, introduced relative to the thickness direction (d) of the molding in the reactive foam.
- At least two fibers (F) in two different angles ⁇ , ai and a 2 introduced, wherein the first angle ⁇ - ⁇ preferably in the range of 0 ° to 15 ° and the second angle a 2 preferably in the range of Is 30 to 50 °, more preferably ai is in the range of 0 ° to 5 ° and a 2 in the range of 40 to 50 °.
- All fibers (F) are preferred at an angle ⁇ in the range of 10 to 70 °, preferably 30 to 60 °, more preferably in the range of 30 to 50 °, even more preferably 30 to 45 °, most preferably 45 ° relative to the thickness direction (d) of the molding introduced into the reactive foam.
- a shaped body according to the invention contains a multiplicity of fibers (F), preferably as fiber bundles, and / or comprises more than 10 fibers (F) or fiber bundles per m 2 , preferably more than 1000 per m 2 , particularly preferably 4000 to 40 000 per m 2 .
- all the fibers (F) in the molding according to the invention have the same angle ⁇ or at least approximately the same angle (deviation of at most + / - 5 °, preferably + / - 2 °, more preferably + / - 1 °).
- All fibers (F) may be present parallel to each other in the molding.
- two or more fibers (F) may be present at an angle ⁇ to one another in the shaped body.
- the angle ⁇ is the angle between the vertical projection of a first fiber (F1) onto the surface of the first side of the shaped body and the perpendicular projection of a second fiber (F2) onto the surface of the shaped body, both fibers are introduced into the molding.
- n is in the range of 2 to 6, more preferably in the range of 2 to 4.
- the angle ⁇ is 90 °, 120 ° or 180 °.
- the angle ⁇ is in the range of 80 to 100 °, in the range of 1 10 to 130 ° or in the range of 170 to 190 °.
- more than two fibers (F) are introduced at an angle ⁇ to one another, for example three or four fibers (F). These three or four fibers (F) can each be to the two adjacent fibers two different angles ß, ß- ⁇ and ß 2 , have. Preferably, all fibers (F) to the two adjacent fibers (F) at the same angle.
- the angle ⁇ is 90 °
- the angle ⁇ i between the first fiber (F1) and the second fiber (F2) is 90 °
- the angle ⁇ 2 between the second fiber (F2) and third fiber (F3) is 90 °
- the angle ⁇ 3 between the third fiber (F3) and the fourth fiber (F4) is 90 °
- the angle ⁇ 4 between the fourth fiber (F4) and the first fiber (F1) is also 90 °.
- the angle ⁇ between the first fiber (F1) (reference) and the second (F2), third (F3) and fourth fiber (F4) is then 90 ° clockwise, 180 ° and 270 °. Analogous considerations apply to the other possible angles.
- the first fiber (F1) then has a first direction
- the second fiber (F2) which is arranged at an angle ß to the first fiber (F1), has a second direction.
- a similar number of fibers Preferably, in the first direction and the second direction, a similar number of fibers.
- similar is meant herein that the difference between the number of fibers in each direction relative to the other direction is ⁇ 30%, more preferably ⁇ 10%, and most preferably ⁇ 2%.
- the fibers or fiber bundles can be introduced in irregular or regular patterns. Preference is given to the introduction of fibers or fiber bundles in regular patterns.
- regular patterns are understood to mean that all fibers are aligned parallel to one another and that at least one fiber or fiber bundle has the same distance (a) to all directly adjacent fibers or fiber bundles all the directly adjacent fibers or fiber bundles at the same distance.
- the first fibers (F1) which are parallel to one another, preferably have a regular pattern with a first spacing (a-1) and the second fibers (F2) which are parallel to each other and are at an angle ⁇ to the first fibers (F1), preferably a regular pattern having a second distance (a 2 ).
- the surface of at least one side of the shaped body has at least one recess, preferably the recess is a slot or a hole, more preferably at least one recess on the surface of at least one side of the Formed body after the implementation of step IV) of the foam molding process, and / or ii) the total surface area of the shaped body to more than 30%, preferably more than 50%, more preferably more than 80%, in particular more than 95 %, closed.
- FIG. 1 shows a schematic representation of a preferred embodiment of the shaped body of reactive foam (1) according to the invention in a perspective view.
- (2) represents (the surface) of a first side of the molding
- (3) represents a second side of the corresponding molding.
- the first side (2) of the shaped body lies opposite the second side (3) of this shaped body.
- the fiber (F) is represented by (4).
- One end of this fiber (4a) and thus the fiber portion (FB1) protrude from the first side (2) of the shaped body, while the other end (4b) of the fiber, which represents the fiber portion (FB3), from the second side (3 ) protrudes the molding.
- the middle fiber region (FB2) is located within the molding and is thus enclosed by the reactive foam.
- the fiber (4) which is for example a single fiber or a fiber bundle, preferably a fiber bundle, is at an angle ⁇ relative to the thickness direction (d) of the shaped body or to the orthogonal (the surface) of the first side (FIG. 2) of the molding.
- the angle ⁇ is 10 to 70 °, preferably 30 to 60 °, particularly preferably 30 to 50 °, especially 30 to 45 °, in particular 45 °.
- F single fiber
- FIG. 3 shows, by way of example, a schematic representation of part of the various angles.
- the shaped body of reactive foam (1) shown in FIG. 3 contains a first fiber (41) and a second fiber (42).
- the first fiber (41) forms a first angle ⁇ ( ⁇ 1) relative to the orthogonal (O) of the surface of the first side (2) of the shaped body.
- the second fiber (42) forms a second angle ⁇ ( ⁇ 2) relative to the orthogonal (O) of the surface of the first side (2).
- the perpendicular projection of the first fiber (41) onto the first side (2) of the shaped body (41 p) forms the angle ⁇ with the perpendicular projection of the second fiber (42) onto the first side (2) of the shaped body (42 p).
- the reactive foam contained in the molded body is produced by a foam molding process.
- the foam molding process comprises the following steps I) to IV).
- step IV) demolding of the expanded foam obtained in step II I) from the forming tool to obtain the reactive foam.
- first component (K1) and second component (K2) contained in the reactive mixture provided in step I) all the first components (K1) and second components (K2) which are capable of reacting with each other are suitable. Such components are known in the art as such.
- isocyanates are suitable. Isocyanates as such are known to the person skilled in the art. In the context of the present invention, isocyanates are understood as meaning all aliphatic, cycloaliphatic and aromatic di- and / or polyisocyanates. Aromatic di- and / or polyisocyanates are preferred. Particularly preferred as the first component (K1) are toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), polymeric diphenylmethane diisocyanates (PMDI) and mixtures thereof. Especially preferred are mixtures of diphenylmethane diisocyanate (MDI) and polymeric diphenylmethane diisocyanates (PMDI) as the first component (K1).
- TDI toluene diisocyanate
- MDI diphenylmethane diisocyanate
- PMDI polymeric diphenylmethane diisocyanates
- K1 isocyan
- isocyanates are used as the first component (K1), these may be modified in whole or in part with uretdione, carbamate, isocyanurate, carbodiimide, allophanate and / or urethane groups. Preferably, they are modified with urethane groups. Such isocyanates are known in the art as such.
- isocyanates are prepolymers and mixtures of the isocyanates and prepolymers described above.
- the prepolymers are prepared from the isocyanates described above and the polyethers, polyesters or mixtures thereof described below.
- Isocyanates suitable as first component (K1) preferably have an isocyanate index in the range from 100 to 400, particularly preferably in the range from 100 to 300, particularly preferably in the range from 100 to 200.
- the isocyanate index is understood as meaning the stoichiometric ratio of isocyanate groups to isocyanate-reactive groups, 20 multiplied by 100.
- Isocyanate-reactive groups are understood to mean all isocyanate-reactive groups present in the reactive mixture, including, if appropriate, chemical blowing agents and compounds containing epoxide groups, but not the isocyanate group itself.
- the second component (K2) used is preferably at least one compound containing isocyanate-reactive groups. Such compounds are known to the person skilled in the art.
- all compounds which have at least two isocyanate-reactive groups such as OH, SH, N H and / or CH-azide groups, can be used as compound with isocyanate-reactive groups.
- Preferred as a second component (K2) is a compound having isocyanate-reactive groups which is selected from the group consisting of
- polyether polyols 35 polyether polyols, polyester polyols and polyamines, wherein the at least one compound having isocyanate-reactive groups having a functionality of 2 to 8 and wherein, when the second component (K2) is selected from polyether polyols and polyester polyols containing at least one compound with isocyanate-reactive groups an average hydroxyl number of
- Polyether polyols as such are known to the person skilled in the art and can be prepared by known processes, for example by anionic polymerization of alkylene oxides with the addition of at least one starter molecule which preferably contains 2 to 6 bonded reactive hydrogen atoms, in the presence of catalysts.
- catalysts alkali metal hydroxides such as sodium or potassium hydroxide or alkali metal such as sodium, sodium or potassium or potassium are used.
- the catalysts used are, for example, Lewis acids such as ammonium pentachloride, boron trifluoride etherate or bleaching earth.
- DMC catalysts double metal cyanide compounds
- amine-based catalysts double metal cyanide compounds
- alkylene oxides one or more compounds having two to four carbon atoms in the alkylene radical such as ethylene oxide, Tetra h yd rofu ran, 1, 2-propylene oxide, 1, 3-propylene oxide, 1, 2-butylene oxide, 2,3-butylene oxide and mixtures from it, used. Preference is given to using ethylene oxide and / or 1,2-propylene oxide.
- starter molecules are ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, glycerol, trimethylolpropane, pentaerythritol, sugar derivatives such as sucrose, hexitol derivatives such as sorbitol, methylamine, ethylamine, isopropylamine, butylamine, benzylamine, aniline, toluidine, toluenediamine, naphthylamine, ethylenediamine, diethylenetriamine, 4 4'-methylenedianiline, 1, 3-propanediamine, 1, 6-hexanediamine, ethanolamine, diethanolamine, triethanolamine and other known to those skilled di- or polyhydric alcohols or mono- or polyhydric amines into consideration.
- polyester polyols are all polyester polyols known to those skilled in the art.
- suitable polyester polyols may be prepared by condensing polyhydric alcohols of two to twelve carbons such as ethylene glycol, diethylene glycol, butanediol, trimethylolpropane, glycerol or pentaerythritol with polyfunctional carboxylic acids having two to twelve carbon atoms, for example, succinic, glutaric, adipic, suberic, azelaic, sebacic, decanedicarboxylic , Maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, the isomers of naphthalenedicarboxylic acids, the anhydrides of said acids, and mixtures thereof.
- aromatic diacids such as phthalic acid, isophthalic acid and / or terephthalic acid and their anhydrides as the acid component and ethylene glycol, diethylene glycol, 1,4-butanediol and / or glycerol as the alcohol component.
- polyfunctional carboxylic acids and corresponding monomeric esters such as dimethyl terephthalate or polymeric esters such as polyethylene terephthalate can be used to prepare the polyester.
- Suitable polyamines are all polyamines known to the person skilled in the art. Suitable polyamines are both aliphatic polyamines and aromatic polyamines. Preference is given to aliphatic polyamines, which are also referred to as polyalkylenepolyamines in the context of the present invention.
- polyalkylenepolyamine is understood as meaning aliphatic amines containing at least three amino groups (primary, secondary or tertiary) .
- Polyethylene polyethylenes are particularly preferably polyethylenimines Homopolymers and copolymers understood which have the groupings -CH 2 -CH 2 -NH- and contain at least three amino groups.
- the first component (K1) and the second component (K2) can react with each other. These reactions are known to those skilled in the art.
- first component (K1) with the second component (K2) for example, form polyurethanes, polyisocyanurates or polyureas, preferably form polyisocyanates or polyurethanes, most preferably form polyurethanes.
- polyurethanes for example, polyurethanes, polyisocyanurates or polyureas, preferably form polyisocyanates or polyurethanes, most preferably form polyurethanes.
- polyurethanes are formed when isocyanates are used as the first component (K1) and polyether polyols as the second component (K2).
- Polyisocyanurates are formed in the use of isocyanates as the first component (K1) and polyester polyols as the second component (K2).
- Polyureas are obtained by the reaction of isocyanates as the first component (K1) and polyamines as the second component (K2).
- polyurethanes may also contain, for example, isocyanurate units, allophanate units, urea units, carbodiimide units, biuret units, uretonimine units and optionally further units which may form as addition reaction of isocyanates as first component (K1).
- polyisocyanurates may, for example, also urethane units, allophanate units, urea units, carbodiimide units, biuret units, uretonimine units and optionally further units which may be in addition reactions of isocyanates as the first component (K1) can form included.
- polyureas for example, can also contain isocyanurate units, allophanate units, urethane units, carbodiimide units, biuret units, uretonimine units and optionally further units which can form as addition reaction of isocyanates as first component (K1).
- step I) The provision of the reactive mixture in step I) can be carried out by all methods known to the person skilled in the art.
- the first component (K1) and the second component (K2) as well as the optional further components and / or catalysts and / or further additives contained in the reactive mixture are usually mixed.
- the mixing takes place for example at a temperature in the range of 15 to 130 ° C, preferably in the range of 15 to 90 ° C, particularly preferably in the range of 25 to 55 ° C.
- the mixing can be carried out by all methods known to the person skilled in the art, for example mechanically by means of a stirrer or a stirring screw or under high pressure in a countercurrent injection method.
- the reactive mixture provided in step I) may also contain further components.
- Other components include physical and / or chemical blowing agents.
- chemical blowing agents are understood to mean blowing agents which are initially present in solid or liquid form in the reactive mixture and then by chemical reaction with the components (K1) and / or (K2), and optionally with others in the reactive one Mix containing components react, forming gaseous products, which then serve as the actual propellant.
- blowing agents are understood to mean blowing agents which, if appropriate under pressure, are dissolved or emulsified in the reactive mixture and evaporate under the conditions in which the reactive mixture reacts.
- Suitable chemical and physical blowing agents are known to those skilled in the art.
- the chemical blowing agents include, for example, water and carboxylic acids, especially formic acid.
- the physical blowing agents include, for example, hydrocarbons, in particular (cyclo) aliphatic hydrocarbons, halogenated hydrocarbons such as perfluorinated alkanes, pentafluorohexane, chlorofluorocarbons, Etheresterketone and acetals, and inorganic and organic compounds that release nitrogen when heated.
- hydrocarbons in particular (cyclo) aliphatic hydrocarbons
- halogenated hydrocarbons such as perfluorinated alkanes, pentafluorohexane, chlorofluorocarbons, Etheresterketone and acetals
- inorganic and organic compounds that release nitrogen when heated.
- Preferred (cyclo) aliphatic hydrocarbons having 4 to 8 carbon atoms are, for example, n-pentane, iso-pentane and cyclopentane.
- the propellant of the reactive mixture is selected from the group consisting of n-pentane, iso-pentane, cyclopentane, 1,1,1,3,3-pentafluorobutane, 1,1,1,3,3-pentafluoropropane, 1,1 , 1, 2,3,3,3-heptafluoropropane, water, formic acid and hydrofluoroolefins, such as 1,1,1,4,4,4-hexafluoro-2-butenes and 1-chloro-3,3,3-trifluoro-propenes , Further preferably, the propellant contains water, more preferably the propellant is water.
- the reactive mixture may contain catalysts.
- catalysts it is possible to use all compounds which accelerate the reaction of the first component (K1) with the second component (K2). Such compounds are known and described for example in "Kunststoffhandbuch Volume 7, polyurethane, Karl Hanser Verlag, 3rd edition 1993, chapter 3.4.1".
- the reactive mixture provided in step I) may contain further additives.
- additives are known in the art as such. Additives are, for example, stabilizers, surface-active substances, flame retardants and chain extenders.
- Stabilizers are also referred to as foam stabilizers.
- stabilizers are understood to be substances which promote the formation of a regular cell structure during foam formation.
- suitable Stabilizers are, for example, silicone-containing foam stabilizers such as siloxane-oxalkylene copolymers and other organopolysiloxanes, and also alkoxylation products of fatty alcohols, oxoalcohols, fatty amines, alkylphenols, dialkylphenols, alkylcresols, alkylresorcinol, naphthol, alkylnaphthol, naphthylamine, aniline, alkylaniline, toluidine, bisphenol A, alkylated bisphenol A , Polyvinyl alcohol and other alkoxylation of condensation products of formaldehyde and alkylphenols, formaldehyde and dialkylphenols, formaldehyde and alkylcresols, formaldehyde and alky
- Surface-active substances are also referred to as surface-active substances.
- Surface-active substances are compounds which serve to assist the homogenization of the starting materials and, if appropriate, are also suitable for regulating the cell structure of the plastics. These include, for example, emulsifiers such as sodium salts of castor oil sulfates or of fatty acids and salts of fatty acids with amines, e.g. diethylamine oleate, diethanolamine stearate, diethanolamine ricinoleic acid, salts of sulfonic acids, e.g. Alkali or ammonium salts of dodecylbenzene disulfonic acid, dinaphthylmethanedisulfonic acid and ricinoleic acid.
- emulsifiers such as sodium salts of castor oil sulfates or of fatty acids and salts of fatty acids with amines, e.g. diethylamine oleate, diethanolamine
- flame retardants for example, organic phosphoric acid and / or phosphonic acid esters can be used. Preference is given to using non-reactive compounds over isocyanate groups. Chlorine-containing phosphoric acid esters are also among the preferred compounds. Suitable flame retardants are, for example, tris (2-chloropropyl) phosphate, triethyl phosphate, diphenyl cresyl phosphate, diethyl ethane phosphinate, tricresyl phosphate, tris (2-chloroethyl) phosphate, tris (1,3-dichloropropyl) phosphate, tris- (2,3-) dibromopropyl) phosphate, tetrakis- (2-chloroethyl) ethylenediphosphate, dimethylmethanephosphonate, diethanolaminomethylphosphonic acid diethyl ester and commercially available halogenated flame retardant polyols.
- bromine-containing flame retardants can be used.
- the bromine-containing flame retardants used are preferably compounds which are reactive toward the isocyanate group.
- Such compounds are, for example, esters of tetrabromophthalic acid with aliphatic diols and alkoxylation products of dibromobutenediol.
- Compounds derived from the brominated, OH group-containing neopentyl compounds may also be used.
- inorganic or organic flame retardants such as red phosphorus, alumina hydrate, antimony trioxide, arsenic oxide, ammonium polyphosphate and calcium sulfate, expandable graphite or cyanuric acid derivatives such as melamine or mixtures of two flame retardants such as ammonium polyphosphates and melamine and optionally corn starch or ammonium polyphosphate, melamine and expandable graphite and / or optionally aromatic polyesters are used to flame-retard the polyisocyanate polyaddition products.
- Chain extenders are understood to mean bifunctional compounds. Such compounds are known in the art as such.
- Suitable chain extenders are, for example, aliphatic, cycloaliphatic and / or aromatic diols having two to fourteen, preferably two to ten carbon atoms, such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-pentanediol, 1,3-pentanediol, 1, 10-decanediol, 1,2-dihydroxycyclohexane, 1,3-dihydroxycyclohexane, 1,4-dihydroxycyclohexane, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, 1,4-butanediol, 1,6-hexanediol and bis (2-hydroxyethyl ) hydroquinone.
- step I I) the reactive mixture provided in step I) is injected into a forming tool. Processes for this are known to the person skilled in the art. Usually, the injection of the reactive mixture into the forming tool is discontinuous.
- the injection of the reactive mixture can be carried out, for example, under elevated pressure.
- the conversion of the reactive mixture, based on the isocyanate groups, during step I I) is preferably less than 90%.
- the amount of reactive mixture injected into the forming tool in step I) is such that the reactive foam obtained in step IV) has the desired overall density and foam structure. If the reactive foam is an integral foam, it is preferred that the degree of compaction is in the range of from 1.05 to 4, preferably in the range of 1.1 to 3.
- the degree of compaction is the ratio of the final density of the reactive foam produced by the foam molding process to the density of the free-foamed reactive foam.
- the forming tool may comprise carrier and / or release layers. Such carrier and / or separating layers are known to the person skilled in the art.
- the carrier and / or release layer is a layer (S2).
- S2 the carrier and / or release layer.
- the embodiments and preferences for the layer (S2) described below apply to this carrier and / or release layer.
- step II I) the reactive mixture is expanded. The expansion of the reactive mixture takes place by the reaction of the first component (K1) with the second component (K2). Such reactions are known in the art. In addition, the expansion may be promoted by the chemical and / or physical blowing agent optionally contained in the reactive mixture.
- the expansion of the reactive mixture may be initiated, for example, by the catalyst optionally contained in the reactive mixture.
- the reactive mixture is expanded to the extent that the resulting expanded foam completely fills the molding tool. Contains the forming tool carrier and / or release layers, so the expanded foam connects to these.
- the mold temperature during step I II) is usually in the range of 20 to 200 ° C, preferably in the range of 30 to 140 ° C, particularly preferably in the range of 30 to 80 ° C.
- the mold temperature during all steps I) to IV) of the foam molding process in the range of 20 to 200 ° C, preferably in the range of 30 to 140 ° C, particularly preferably in the range of 30 to 80 ° C.
- step IV the expanded foam obtained in step I II) is removed from the forming tool to obtain the reactive foam.
- the foam molding process for producing the reactive foam is preferably carried out as a one-shot process, particularly preferably using the low-pressure technique or the high-pressure technique. In this case, usually closed and optionally tempered shaping tools are used.
- the one-shot process for polyurethanes is described, for example, by Piechota and Rschreib in "Integralschaumstoff", Carl Hanser Verlag, Kunststoff, Vienna, 1975, or in the "Kunststoffhandbuch", Volume 7, Polyurethane, 3rd edition, 1993, Chapter 7.
- a one-shot method is known to those skilled in the art. In the one-shot method, steps I) and II) are carried out directly one after the other or simultaneously.
- the first component (K1) and the second component (K2) present in the reactive mixture and, if appropriate, the further components, the catalyst and the further additives are mixed with one another during the injection into the shaping tool, for example in US Pat a static or dynamic mixer.
- the resulting reactive foam can be processed optionally after cutting and / or thermally in connection with step IV). Methods for this purpose are known to those skilled in the art. Preferably, after removal from the mold in accordance with step IV), no cutting and / or thermal processing of the reactive foam takes place.
- the length of the reactive foam thus obtained is referred to as the x-direction, the width as the y-direction and the thickness as the z-direction.
- the reactive foam of the invention may have any size.
- the reactive foam produced according to the invention has a thickness (z-direction) in the range of 4 to 200 mm, preferably in the range of 5 to 60 mm, a length (x-direction) of at least 200 mm, preferably of at least 400 mm and a width (y-direction) of at least 200 mm, preferably of at least 400 mm.
- the reactive foam usually has a length (x-direction) of not more than 4000 mm, preferably of not more than 2500 mm, and / or a width (y-direction) of not more than 4000 mm, preferably of not more than 2500 mm.
- the reactive foam is preferably based on a polyurethane, a polyurea or a polyisocyanurate. Particularly preferred is the reactive foam based on a polyurethane.
- the reactive foam based on a polyurethane, a polyurea or a polyisocyanurate it means in the present invention that the reactive foam in addition to the polyurethane, polyurea or polyisocyanurate may contain other polymers, for example as a blend of the polyurethane, the polyurea or the polyisocyanurate and another polymer. Processes for the preparation of these blends are known to the person skilled in the art. If the reactive foam based on a polyurethane, it is also preferred that it is a polyurethane foam, in particular a Semi-rigid polyurethane foam, a flexible polyurethane foam or a polyurethane rigid foam.
- the reactive foam is based on a polyurethane, a polyurea or a polyisocyanurate, which is prepared in each case by a foam molding process comprising the abovementioned steps I) to IV), and in which the reactive Mixture as the first component (K1) at least one polyisocyanate and as a second component (K2) at least one compound containing isocyanate-reactive groups and as further component at least one blowing agent.
- the reactive foam based on a polyurethane prepared by a foam molding process comprising the above-mentioned steps I) to IV) and wherein the first component (K1) is selected from diphenylmethyl diisocyanate and polymeric diphenylmethane diisocyanate and the second component (K2 ) is at least one compound having isocyanate-reactive groups which is selected from the group consisting of polyether polyols, polyester polyols and polyamines, wherein the at least one compound having isocyanate-reactive groups has a functionality of 2 to 8 and wherein when the second component ( K2) is selected from polyether polyols and polyester polyols having at least one compound having isocyanate-reactive groups an average hydroxyl number of 12 to 1200 mg KOH / g and the reactive mixture comprises a further component containing at least one propellant containing water.
- the first component (K1) is selected from diphenylmethyl diisocyanate and polymeric diphenylmethane diis
- the reactive foam usually has a glass transition temperature of at least 80 ° C., preferably of at least 110 ° C. and more preferably of at least 130 ° C., determined by differential scanning calorimetry (DTA).
- the glass transition temperature of the reactive foam is generally not more than 400 ° C., preferably not more than 300 ° C., in particular not more than 200 ° C., determined by means of differential thermal analysis (DTA).
- the subject of the present invention is also a panel comprising at least one shaped body according to the invention and at least one layer (S1).
- a “panel” may also be referred to in the art as “sandwich”, “sandwich material”, “laminate” and / or “composite article”.
- the panel has two layers (S1), and the two layers (S1) are each attached to one side of the shaped body opposite to the other side in the molded body.
- the layer (S1) comprises at least one resin, preferably the resin is a reactive thermosetting or thermoplastic resin, more preferably the resin is based on epoxides, acrylates, polyurethanes, polyamides, polyesters, unsaturated polyesters, vinyl esters or mixtures thereof, in particular the resin is an amine-curing epoxy resin, a latent curing epoxy resin, an anhydride-curing epoxy resin or a polyurethane of isocyanates and polyols.
- resin systems are known to the person skilled in the art, for example from Penczek et al. (Advances in Polymer Science, 184, pp. 1-95, 2005), Pham et al. (Ullmann's Encyclopedia of Industrial Chemistry, Vol. 13, 2012), Fahnler (Polyamides, Plastics Handbook 3/4, 1998) and Younes (W012134878 A2).
- a panel in which i) the fiber region (FB1) of the fiber (F) is partially or completely, preferably completely, in contact with the first layer (S1), and / or ii) the fiber region (FB3) Fiber (F) is partially or completely, preferably completely, in contact with the second layer (S1), and / or iii) the panel has at least one layer (S2) between at least one side of the shaped body and at least one layer (S1),
- the layer (S2) of sheet-like fiber materials or polymeric films more preferably of porous sheet-like fiber materials or porous polymeric films, particularly preferably of paper, glass fibers or carbon fibers in
- Porosity is the ratio (dimensionless) of void volume (pore volume) to the total volume of a reactive foam. It is determined for example by image analysis of microscopic images by the void or pore volume is divided by the total volume.
- the total porosity of a substance is made up of the sum of the voids that communicate with each other and the environment (open porosity) and the non-interconnected voids (closed porosity). Preference is given to layers (S2) which have a high open porosity.
- the at least one layer (S1) additionally comprises at least one fibrous material, i) the fibrous material comprising fibers in the form of one or more layers of cut fibers, nonwovens, loops, knits and / or fabrics, preferably in
- the fibrous material comprises fibers of organic, inorganic, metallic or ceramic fibers , preferably polymeric fibers, basalt fibers, glass fibers, carbon fibers or natural fibers, particularly preferably glass fibers or carbon fibers.
- the natural fibers and the polymeric fibers apply the previously described embodiments.
- a layer (S1) which additionally contains at least one fibrous material is also referred to as a fiber-reinforced layer, in particular as a fiber-reinforced resin layer, if the layer (S1) comprises a resin.
- FIG. 2 shows another preferred embodiment of the present invention.
- an inventive panel (7) is shown, which comprises a molded body (1) according to the invention, as shown for example in the context of the embodiment of FIG.
- the reference numerals in other abbreviations in Figures 1 and 2 have the same meaning.
- the panel according to the invention comprises two layers (S1), which are represented by (5) and (6).
- the two layers (5) and (6) are thus located on mutually opposite sides of the shaped body (1).
- the two layers (5) and (6) are preferably resin layers or fiber-reinforced resin layers.
- the two ends of the fiber (4) are enclosed by the respective layer (5) or (6).
- one or more further layers may be present between the shaped body (1) and the first layer (5) and / or between the shaped body (1) and the second layer (6).
- a single fiber (F) is represented by (4).
- a panel is preferred in which at least one of the following alternatives is fulfilled: i) the molded body contained in the panel contains at least one side which has not been mechanically and / or thermally processed, and / or ii) comprises the molded body contained in the panel at least one layer (S2) which was applied as a carrier film to the reactive foam in the foam-forming process comprising steps I) to V) in step II), and / or iii) the at least one layer (S1) comprises a resin and the reactive foam of the shaped body has a resin absorption of less than 1000 g / m 2 , preferably less than 500 g / m 2 and particularly preferably less than 100 g / m 2 , and / or iv) the panel has a peel strength of more than 200 J / m 2 , preferably of more than 500 J / m 2 , more preferably of more than 2000 J / m 2 , and / or v) the reactive foam of the molding contained in the panel has
- the molded body contained in the panel has a specific shear strength measured in parallel to the at least a layer (S1) of at least
- the molding contained in the panel has in Panel a shear modulus measured parallel to the at least one layer (S1) of at least 0.2 MPa / (kg / m 3 ), preferably of at least 0.6 MPa / (kg / m 3 ), more preferably of at least 1, 0 MPa / (kg / m 3 ), on.
- the specific shear strength and the shear modulus are determined according to DI N 53294 (as of 1982) and the density according to ISO 845 (as of 2007).
- the shear modulus of the molding according to alternative vi) refers to the shear modulus of the molding without the at least one layer (S1). Only the measurement takes place parallel to the side at which the at least one layer (S1) is applied in the panel.
- the peel strength of the panel is determined with single cantilever beam (SCB) samples.
- the thickness of the moldings is 20 mm, the layers (S1) each consist of about 2 mm thick quasi-isotropic glass fiber reinforced epoxy resin.
- the panels are then tested in a Zwick Z050 tensile testing machine at a speed of 5 mm / min, loading and unloading the panel three to four times.
- the crack growth or the increase in each load cycle (Aa) is determined optically.
- the crack growth energy (AU) is determined from the force-displacement curve. From this, the fracture toughness or peel strength is determined as
- the reactive foam and glass gels are used in addition to the resin systems used, the reactive foam and glass gels: nylon vacuum film, vacuum sealing tape, nylon flow aid, polyolefin release film, polyester tear off fabric and PTFE membrane film and polyester absorbent nonwoven.
- Panels also referred to below as sandwich materials, are produced from the moldings by applying fiber-reinforced cover layers by means of vacuum infusion.
- At the top and bottom of the (fiber-reinforced) foams are each two layers of Quadrax Glasgelege (Roving: E-Glass SE1500, OCV, textile: Saertex, isotropic laminate [0 -45 90 ° 45 °], each 1200 g / m 2 ) applied.
- a release film is inserted between the molded body, hereinafter also referred to as core material, and the glass scrim, in contrast to the standard production of the panels.
- core material hereinafter also referred to as core material
- the glass scrim On the glass shelves the tear-off fabric and the flow aids are attached on both sides.
- the assembly is then fitted with sprues for the resin system and ports for evacuation. Finally, a vacuum film is applied over the entire structure, sealed with sealing tape and evacuated the entire structure.
- the structure is prepared on an electrically heated table with a glass surface.
- the resin system used is amine-curing epoxy (resin: BASF Baxxores 5 5400, hardener: BASF Baxxodur 5440, mixing ratio and further processing according to data sheet).
- the resin is evacuated for 10 minutes at up to 20 mbar.
- a resin temperature of 23 + / - 2 ° C infusion takes place on the pre-tempered structure (table temperature: 35 ° C).
- temperature ramp of 0.3 K / min from 35 ° C to 75 ° C and isothermal0 curing at 75 ° C for 6 h panels can be made, which consist of the reactive foams and glass fiber reinforced cover layers.
- the moldings are measured according to ISO 845 (as of October 2009) in order to obtain the density of the molded body.
- the processed panels are trimmed to eliminate excess resin build-up in the peripheral areas by non-conforming vacuum foil.
- the cover layers are removed and the moldings contained are measured again by ISO 845.
- the difference between the densities results in the absolute resin absorption.
- the corresponding resin absorption results in kg / m 2 .
- the present invention furthermore relates to a process for producing the shaped body according to the invention, wherein at least one fiber (F) is partially introduced into the reactive foam, whereby the fiber (F) with the fiber region (FB2) is located inside the shaped body and enclosed by the reactive foam is, while the fiber region (FB1) of the fiber (F) protrudes from a first side of the shaped body and the fiber region (FB3) of the fiber (F) protrudes from a second side of the shaped body.
- the partial introduction of the at least one fiber (F) into the reactive foam by sewing using a needle preferably the partial introduction of steps a) to f): 0 a) optionally applying at least one Layer (S2) on at least one side of the reactive foam, b) producing one hole per fiber (F) in the reactive foam and optionally in the layer (S2), the hole extending from a first side to a second side of the reactive foam and optionally through the layer (S2), c) providing at least one fiber (F) on the second side of the reactive foam, d) passing a needle from the first side of the reactive foam through the hole to the second side of the reactive foam and optionally passing the needle through the layer (S2), e) affixing at least
- Layer (S2) protrudes and the fiber region (FB3) of the fiber (F) protrudes from a second side of the molding, more preferably, the steps b) and d) are carried out simultaneously.
- step a) The application of at least one layer (S2) in step a) can be carried out, for example, as described above during step II) of the foam molding process.
- steps b) and d) are carried out simultaneously.
- the hole is created from the first side to the second side of the reactive foam by passing a needle from the first side of the reactive foam to the second side of the reactive foam.
- the introduction of the at least one fiber (F) may comprise, for example, the following steps: a) optionally applying a layer (S2) to at least one side of the reactive foam, b) providing at least one fiber (F) on the second side of the reactive foam; c) producing one hole per fiber (F) in the reactive foam and optionally in the layer (S2), the hole being from the first side to a second one Side of the reactive foam and optionally through the layer (S2) and wherein the hole is created by passing a needle through the reactive foam and optionally through the layer (S2), d) attaching at least one fiber (F) to the needle e) recycling the needle and fiber (F) through the hole so that the fiber (F) is in the body portion with the fiber portion (FB2) and
- Reactive foam is enclosed, while the fiber region (FB1) of the fiber (F) protrudes from a first side of the shaped body or optionally from the layer (S2) and the fiber region (FB3) protrudes from a second side of the shaped body, f) optionally cutting off the fiber (F) on the second side and g) optionally cutting open the loop of the fiber (F) formed on the needle.
- a hook needle is used as the needle and at least one fiber (F) hooked into the hook needle in step d).
- a plurality of fibers (F) are simultaneously introduced into the reactive foam according to the previously described steps.
- depressions in the shaped body are introduced partially or completely into the reactive foam before the introduction of at least one fiber (F).
- the present invention further provides a process for the production of the panel according to the invention, in which the at least one layer (S1) is produced, applied and cured as reactive viscous resin on a molded body according to the invention, preferably by liquid impregnation, more preferably by pressure or vacuum assisted impregnation, especially preferably by vacuum infusion or pressure assisted injection methods, most preferably by vacuum infusion.
- liquid impregnation methods are known to the person skilled in the art and are described, for example, in Wiley Encyclopedia of Composites (2nd Edition, Wiley, 2012), Parnas et al. (Liquid Composite Molding, Hanser, 2000) and Williams et al. (Composites Part A, 27, pp. 517-524, 1997).
- auxiliary materials can be used to produce the panel according to the invention.
- Suitable auxiliary materials for production by vacuum infusion are, for example, vacuum film, preferably nylon, vacuum sealing tape, flow aid, preferably nylon, release film, preferably polyolefin, tear-off fabric, preferably polyester and a semipermeable film, preferably a membrane film, more preferably a PTFE membrane film and Absaugvlies , preferably of polyester.
- the choice of suitable auxiliary materials depends on the component to be manufactured, the selected process and the materials used, especially the resin system. When using resin systems based on epoxy and polyurethane, preference is given to using nylon flow aids, polyolefin release liners, polyester tear-off fabrics and semipermeable films as PTFE membrane sheets and polyester absorbent sheets.
- auxiliary materials can be used in various ways in the processes for producing the panel according to the invention.
- Panels are particularly preferably produced from the moldings by applying fiber-reinforced cover layers by means of vacuum infusion.
- fibrous materials and optionally further layers are applied to the upper and lower sides of the molded bodies to produce the panel according to the invention.
- tear-off fabric and release films are placed.
- infusion of the liquid resin system can be used with flow aids and / or membrane films.
- VAP structure semipermeable membrane
- VAP structure semipermeable membrane
- release film and Abr facedgewebe be used on one or both sides and the semipermeable membrane is sealed by vacuum sealing tape to the mold surface, the Absaugvlies is used on the molding foreign side of the semipermeable membrane whereby the air surface is evacuated to the top
- a membrane bag vacuum bag which is preferably placed on the opposite sprue side of the molded body, evacuating the air from the opposite side to the gate.
- the assembly is then fitted with sprues for the resin system and ports for evacuation. Finally, a vacuum film is applied over the entire structure, sealed with sealing tape and evacuated the entire structure. After infusion of the resin system, the reaction of the resin system takes place while maintaining the vacuum.
- the present invention furthermore relates to the use of the shaped body or the panel according to the invention for rotor blades, in wind turbines, in the transport sector, in the construction sector, in the automotive industry, in shipbuilding, in rail vehicle construction, for container construction, for sanitary facilities and / or in the aerospace industry. and space travel.
- Example 1 Comparative Example: Moldings of Reactively Produced PU Molded Foams Without Fiber Reinforcement The following components were used:
- K1 -1 Mixture of diphenylmethane diisocyanate and polymethylene phenyl polyisocyanate with an isocyanate index of 130 and a
- Viscosity of 200 mPa ⁇ s at 25 ° C. (according to DIN 53019)
- K2-2 polypropylene oxide having a functionality of 2, a number average molecular weight M n of 1000 g / mol and a viscosity of 150 mPa ⁇ s
- K2-3 pentaerythritol-based ethylene oxide having a functionality of 4, a number average molecular weight M n of 350 g / mol and a viscosity of 1000 mPa ⁇ s at 25 ° C .;
- K2-4 phthalic anhydride / diethylene glycol-based with a functionality of 2, a number average molecular weight M n of 350 g / mol and a viscosity of 2500 mPa ⁇ s at 25 ° C. (according to DI N 53019)
- Catalyst tertiary aliphatic amine
- A-1 chain extender: propylene glycol based, weight average
- A-2 Crosslinker: Glycerol-based, weight-average molecular weight M w of 94 g / mol
- A-3 Stabilizer: Silicone-containing stabilizer for rigid polyurethane foam
- the preparation of the reactive polyurethane foam according to the invention is carried out by the discontinuous foaming of the reactive mixtures in a mold.
- the second component (K2) and the other additives, the catalyst and the other components are introduced, the first component (K1) is added and the mixture is mixed at room temperature with a suitable stirrer at 1800 U / min in an open vessel.
- the parts by weight of the components are given in Table 1.
- the resulting reactive mixture is then introduced into a suitably tempered mold at 45 ° C and cured to obtain a rigid polyurethane foam.
- the polyurethane rigid foam obtained is cut into the required shape for further processing.
- the basic geometry of the moldings obtained is given by the forming tool and described in more detail in the further description.
- Table 1 Component parts by weight
- the reactive foam and glass gels are used in addition to the resin systems used, the reactive foam and glass gels: nylon vacuum film, vacuum sealing tape, nylon flow aid, polyolefin release film, polyester tear off fabric and PTFE membrane film and polyester absorbent nonwoven.
- Panels also referred to below as sandwich materials, are produced from the moldings by applying fiber-reinforced cover layers by means of vacuum infusion.
- At the top and bottom of the (fiber-reinforced) foams are each two layers of Quadrax Glasgelege (Roving: E-Glass SE1500, OCV, textile: Saertex, isotropic laminate [0 -45 90 ° 45 °], each 1200 g / m 2 ) applied.
- a release film is inserted between the molded body, hereinafter also referred to as core material, and the glass scrim, in contrast to the standard production of the panels.
- core material a molded body
- the glass scrim On the glass shelves the tear-off fabric and the flow aids are attached on both sides. The assembly is then fitted with sprues for the resin system and ports for evacuation. Finally, a Applied vacuum film over the entire structure, sealed with sealing tape and evacuated the entire structure.
- the structure is prepared on an electrically heated table with a glass surface.
- the resin system used is amine hardening epoxy (resin: BASF Baxxores 5400, hardener: BASF Baxxodur 5440, mixing ratio and further processing according to data sheet).
- the resin is evacuated for 10 minutes at up to 20 mbar.
- a resin temperature of 23 + / - 2 ° C infusion takes place on the pre-tempered structure (table temperature: 35 ° C).
- subsequent temperature ramp of 0.3 K / min from 35 ° C to 75 ° C and isothermal curing at 75 ° C for 6 h panels can be made, which consist of the reactive foams and glass fiber reinforced cover layers.
- the moldings are measured according to ISO 845 (as of October 2009) in order to obtain the density of the molded body.
- the processed panels are trimmed to eliminate excess resin build-up in the marginal areas by improperly fitting vacuum foil.
- the cover layers are removed and the moldings contained are measured again by ISO 845.
- the difference of the densities results in the absolute resin absorption.
- the corresponding resin absorption results in kg / m 2 .
- V4 slotted plate by cutting ⁇ 5% 3.8 kg / m 2
- Example 1 In order to improve the peel strength at the same time low resin absorption at the surface, the experiments of Example 1 are repeated, however, the molded body (reactive foam) is initially partially reinforced with glass fibers (rovings, S2-glass, 400 tex, AGY).
- the glass fibers are introduced in the form of rovings at an angle ⁇ of 45 ° in four different spatial directions at an angle ⁇ to each other (0 °, 90 °, 180 °, 270 °). In all spatial directions, an identical number of glass fibers is introduced.
- about 10 mm of the glass fibers are left on the cover layer on the supernatant on both sides in order to improve the connection to the glass fiber mats later introduced as cover layers.
- the fiber or fiber rovings are introduced automatically by a combined sewing / crochet process.
- a hook needle (diameter approx. 0.80 mm) is pierced completely from the first side to the second side of the particle foam.
- a roving is hooked into the hook of the hook needle and then pulled from the second side through the needle back to the first side of the reactive foam.
- the roving on the second side is cut off and the formed roving loop is cut on the needle.
- the hook needle is thus ready for the next process.
- the peel strength of the panels is determined with single cantilever beam (SCB) samples.
- the thickness of the moldings is 20 mm, the layers (S1) each consist of about 2 mm thick, quasi-isotropic glass fiber reinforced epoxy resin. This results in a thickness of the panel of 24 mm.
- the samples are tested in a Zwick Z050 tensile testing machine at a speed of 5 mm / min, whereby each test piece is loaded and unloaded several times (3 to 4 times).
- the crack growth or the increase in each load cycle (Aa) is determined optically. From the Force-displacement curve determines the crack growth energy (AU). From this, the fracture toughness or peel strength is determined as
- the peel strength in a panel can be increased significantly (B7 to B10) by means of the moldings with integrated fibers comprising a reactively produced PU molded foam according to the invention.
- the fiber reinforcement of the reactive foam thus allows for a nearly identical resin absorption of the surface a significant increase in the peel strength.
- the strength depends only slightly on the surface roughness or pretreatment and thus allows a decoupling of the two optimization goals peel strength and resin absorption.
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Abstract
Description
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PCT/EP2017/061869 WO2017202668A1 (en) | 2016-05-25 | 2017-05-17 | Fibre reinforcement of reactive foams obtained by a moulding foam method |
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EP3464433B1 (en) | 2016-06-07 | 2020-11-18 | Basf Se | Method for manufacturing expandable granulates containing polylactic acids |
ES2841779T3 (en) | 2016-08-26 | 2021-07-09 | Basf Se | Process for the continuous production of fiber-reinforced foams |
CN109851740A (en) * | 2019-01-22 | 2019-06-07 | 安徽中科都菱商用电器股份有限公司 | The foamed heat-insulating material and preparation method thereof of medical ultra low temperature freezer |
MA54957A (en) | 2019-02-14 | 2022-02-09 | Build Ip Llc | ENCLOSURE COMPONENT PERIMETER STRUCTURES |
BR112021013428B1 (en) * | 2019-08-06 | 2023-12-05 | MAFTEC Co., Ltd | ARTICLE MADE OF INORGANIC FIBER, BLANKET FOR A DISCHARGE GAS CLEANING APPARATUS AND DISCHARGE GAS CLEANING APPARATUS |
US11739547B2 (en) | 2021-01-12 | 2023-08-29 | Build Ip Llc | Stackable foldable transportable buildings |
US11718984B2 (en) | 2021-01-12 | 2023-08-08 | Build Ip Llc | Liftable foldable transportable buildings |
CN118749004A (en) * | 2022-03-04 | 2024-10-08 | 亨斯迈国际有限责任公司 | Sustainable polyester polyols and uses thereof |
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2017
- 2017-05-17 WO PCT/EP2017/061869 patent/WO2017202668A1/en active Search and Examination
- 2017-05-17 US US16/303,491 patent/US11613620B2/en active Active
- 2017-05-17 CN CN201780032541.4A patent/CN109196031B/en active Active
- 2017-05-17 ES ES17723145T patent/ES2891775T3/en active Active
- 2017-05-17 EP EP17723145.3A patent/EP3464437B1/en active Active
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CN109196031A (en) | 2019-01-11 |
CN109196031B (en) | 2022-01-28 |
ES2891775T3 (en) | 2022-01-31 |
US20200317880A1 (en) | 2020-10-08 |
EP3464437B1 (en) | 2021-07-07 |
US11613620B2 (en) | 2023-03-28 |
WO2017202668A1 (en) | 2017-11-30 |
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